DE2646145A1 - ARTICLES MADE OF PHENOLIC RESIN AND PROCESS FOR THEIR PRODUCTION - Google Patents

Description

DipL-Ing. A. Spalthoff ^D " ^{43 Essen x de} * 25. 1 ^ 76

Patent attorney Pelmanstrafle 31

Box 1533 2 G 4 G 1 4 0 Telephone (0201) 772008

File no. 22 636 B / G. please indicate in the answer

GOMPOX) IR DES PLASTIQUES, VIRIEU-LE-GRAND (AIN), FRANCE

Phenolic resin articles and processes for their manufacture

Me invention relates to a process for the production of molded parts or articles based on Phenolic resins or resol by simultaneous injection of at least one resin of the aforementioned type, reinforcing elements made of glass, and of at least one acidic catalyst as main components in a mold. Known to be used one for the production of shaped pieces apparatuses ζμιη simultaneous Injection of liquid phenolic resins, resole and

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Dipl.-Ing. A. Spalthoff, patent attorney, 43 Essen

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of crushed glass for reinforcement. However, it is necessary to use some of the elements of conventional machines, otherwise were attacked by the acidic catalysts, to be replaced by elements made of acid-resistant material.

However, the moldings obtained were not entirely satisfactory, both with regard to their mechanical properties and their behavior in fire or their fire resistance for a given thickness and percentage of reinforcing glass.

Namely, phenolic resin in the resole state generally contains 12 to 15 percent by weight of water, and in the condensation reaction that causes the finished product to harden leads, additional water is released.

This water is difficult to eliminate from the finished piece and affects the complete condensation of the resin. A heat treatment is necessary, which takes place below 100 ° C must so that the water trapped in the piece does not suddenly evaporate. By leaving Finally, water is given a more or less microporous structure, which increases the mechanical properties as well

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DipL-Ing. A. Spalthofiv patent attorney, 43 Essen

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the aging resistance will be impaired.

As is known, phenolic resins are excellent Fire resistance on; so you can, for example, with a layered plastic from 3O / 6 glass and these resins a classification Mt-. Achieve in the Fe-u-test. It is also known that the fire resistance by adding inorganic Substances to the composition can be improved. This addition of inorganic substances, however, takes a long time and costly mixing operations. Such operations affect the uniform distribution of the reinforcement elements made of glass, which leads to products whose fire resistance is improved, but the mechanical resistance is inferior Have properties · Before changing inorganic additives in an unfavorable way the viscosity of the starting mixture and the water content

After thorough research - for the purpose of. Elimination The applicant suffers from the above-mentioned disadvantages of known methods an ib ues manufacturing process based on liquid phenolic resins or resoles created for molded parts, which can be produced by simultaneously injecting the resins, the Reinforcement elements made of glass and acid catalyst as Main components received in a mold.

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Dipl.-Ing. A. Spalthoff, patent attorney, 43 Essen

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The task set is achieved by the above-mentioned method Invention according to the fact that one simultaneously with the the aforementioned main constituents at least one inorganic, anhydrous and hydrophilic compound is added, the amount of which between 8 and 12 percent by weight of the liquid phenolic resin «

The invention also relates to and extends to "apparatus for performing this method." on the molded pieces and parts obtained, which are characterized by improved mechanical properties and fire resistance distinguish.

As a starting material can use any liquid phenolic resin or resole, and any inorganic, hydrophilic compound, such as semi-hydrated calcium hydroxide (SO ^ Ga) ₂ Ho ⁰ * ^ias ^ - ^m sold under the name "plaster" is available. Three water molecules can be added per molecule of this compound according to the following reaction formula: (SO ^ Ca) ₂ H ₂ O + 3H ₂ O -> 2 (SO ₄ Ca ₂ H ₂ O)

Another object of the invention is to eliminate the disadvantage arising from the fact that commercially available, semi-hydrogenated calcium sulfates, e.g. more common

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Dipl.-Ing. A. Spalthoff, patent attorney, 43 Essen

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Plaster of paris cannot be used because it contains a certain amount of carbonate, which is the case with an acidic catalyst Development of carbon gases. This gas evolution brings about a foam formation, as well as an expansion of the plastic layer, which in turn is the task would contradict the invention to achieve a homogeneous resin-glass laminate without bubbles or other "fish eyes".

According to the invention, the calcium sulfate is neutralized starting from Sulfuric acid obtained and then removed from it at a temperature of about 130 ° C. These The temperature limit must not be exceeded, otherwise irreversible, anhydrous calcium sulphate is formed.

According to another exemplary embodiment according to the invention, finely divided boric anhydride is used as the inorganic, hydrophilic anhydride; in the presence of the water contained in the resol and formed from the condensation, the following reaction takes place: B ₂ O ₃ + 3 H ₂ O - ^ 2 B (OH) ₃

In other words, 1 gram molecule of boric anhydride

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Dipl.-Ing. A. Spalthoii, patent attorney, 43 Essen

agrees with 5 ^ grams of water, on condition that that boric anhydride used is well distributed at the moment of simultaneous injection.

The addition of the inorganic hydrophilic compound must take place during the simultaneous injection, not the previous one Mixing with the resol, for the following two main reasons:

- maintaining a suitable viscosity of the resin,

which is the prerequisite for good injection and wetting of the glass.

- the dehydrating action of the inorganic hydrophilic substance at the moment of condensation, and not already on the water of the original mixture of liquid resole resin.

The water released by the condensation is thus most completely absorbed by the action of the anhydrous inorganic substances at the last moment, which causes the free amount of water contained in the finished molded part is reduced to a minimum.

The invention also relates to a device for carrying out the method according to the invention:

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Dipl.-Ing. A. Spalthoff, patent attorney, 43 Essen

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■ si

This device consists of: a pneumatically operated device for injecting the resin and the Catalyst, on the one hand with a glass fiber chopping and shredding device coupled to pneumatic means cooperates, and on the other hand with associated electromagnetic and pneumatic means for dining with deshydrating powder, with commissioning and shutdown of the three aforementioned units is controlled by an electrical relay device, which is also is provided for regulating the powder throughput depending on the throughput of the other components.

This device for simultaneous injection, described in more detail below, enables:

- the addition of the anhydrous mineral salts at the moment the injection itself, rather than the initial resin mix; .

- the adjustment of the proportion of mineral salts to the injection speed in order to keep the dosage constant at the same Hold setpoint;

- an even distribution of the mineral salts each point of the total mass of the laminate making up the final product.

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Dipl.-Ing. A. Spalthoff, patent attorney, 43 Essen

In the following, a device according to the invention is explained in more detail with reference to the accompanying drawing.

In the drawing is a continuous distribution and metering device that operates by electromagnetic vibration shown, which consists of a vibrator 1 with a power control resistor (not shown in the drawing); above a container 2 is attached, the destiydrierende Powder contains urd. Opens into a funnel 3; the Unit is supported by a 4-pillar. In the lower chute 3A of the funnel 3 opens an air injection nozzle of the "Giffard" type, the air jet of which is axially against an elastic Tube 5 is directed towards, on the one hand to the lower end of the chute 5A and on the other oeite is connected to an end piece 6, which is firmly connected to a fiberglass chopper and shredder 7, which in turn is shot at a spray gun 8.

In operation, the powder introduced into the container 2 becomes exposed to the vibrations, ascends on a spiral path provided in the container (in the drawing not shown), and falls through a channel 2A into the funnel 3 »at the outlet of which it falls through the hose 5 to the

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Dipl.-Ing. A. Spalthoif, patent attorney, 43 Essen

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End piece 6 is conveyed, at the exit of which it is during simultaneous injection with the resin and catalyst stream mixes, which comes from the spray gun 8, as well as with the coming from the glass cutting and crushing apparatus, crushed Glass. This apparatus consists of a housing in which one of means for compressed air supply (in the drawing not shown) actuated cylinder 7A is attached, the a cylinder 7B made of rubber, which in turn operates the Actuated cutting cylinder for glass fibers or "roving" glass.

The simultaneous starting and stopping of the distribution and vibration device 1, the Giffard apparatus 10, the Cutting and comminuting device 7 and the spray gun 8 are controlled by an electrical relay device (not shown in the drawing), which under among other things, the powder throughput depending on the relevant Controls throughputs of glass and resin.

This system allows an exact dosage of the amount of water-attracting anhydride salts that are not bound with the Water in the fittings react.

According to the invention, the conventional method of bladder

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Dipl.-Ing. A. Spalthofi, patent attorney, 43 Essen

distance not changed with this method. When the piece comes out of the mold, it is preferably heated to 70 to 80 ^° C.

Thanks to the anhydride salts, the heating-up time can be reduced by about 50 #; the homogeneity of the piece is improved, by suppressing the development of small bubbles, which is the case with the known techniques of discharging water originate from; finally, the fire resistance of the produced pieces is improved.

The invention is explained in more detail in the following examples for processing and testing:

1. Preparation when using a finely ground boron anhydride (B ₂ O ₅ ).

The commercially available boron anhydride crystals are fed into a horizontal, rotating hammer mill; the grinding process takes 3 hours at a speed of 60 rpm. As a result of the hydrogenation of boric anhydride the boric acid is preserved, and the resole is crosslinked under the action of the acidic catalysts, brings the use of additives based on boric anhydride the emergency

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Dipl.-Ing. A. Spalthoff, patent attorney, 43 Essen

agility to reduce the amount of catalyst injected, if one wants to maintain a sufficiently long deflation time after the simultaneous injection # So can for example, in the case of cold mixing, in which the amount of catalyst is generally fixed at 20 parts (this number applies for a commercially available mixture without admixture) this amount of catalyst can be reduced to 15 to 18 parts if you use the invention 5 to 8 parts of finely ground boric anhydride adds. The life of the injected mixture then remains at around 30 minutes.

2. Preparation of two starting mixes for the Manufacture of laminates.

In order to better emphasize the excellent properties of the laminates obtained according to the invention, two starting mixtures have been prepared.

Mixture A is the comparison mixture for mixture B in which the admixture or addition according to the invention is used which influences the condensation reaction in such a way that it proceeds more completely.

Mixture A

Resophen PL 5.600 from Rhone Poulenc 100 parts

Hardener P 5.001 from Bhfine Poulenc 20 parts

Roving glass, cut 5 cm, from St-Gobain 25 parts

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Dipl.-Ing. A. Spaithoif, patent attorney, 43 Essen

The Resophen PL · 5.600 from Rhone Poulenc is aue the formol-phenol condensation in a ratio greater than 1, in an alkaline medium with the formation of a linear chain in a 9-10 # aqueous solution.

The hardener P 5-001 from Rhone Poulenc is a ke-reticulating agent Phenol-sulphonic acid type catalyst.

Mixture B

Resophen PL 5.600 from Rhone Poulenc 100 parts

Hardener P 5.001 from Rhone Poulenc 16 parts Grind-es B ₂ O ^ ^from Borax-Francais 8 parts

Roving glass, cut 5cm, from St-Gobain 25 pieces 3- Preparation of the test pieces

Based on mixtures A and B, two test models are produced:

a) Test pieces of 150 χ 15 x 4 m / m »on those after

the heating for 24 hours at 80 ⁰ G the characteristics: external appearance, shrinkage, weight loss, flexural modulus under load E = - according to the French standard NFT

4Zh3f FL

57.105, as well as bending stress under load r - 1.5

according to the French norm N.F.T. 57 105 are examined, b) Test pieces of 150 χ 6 χ 3 m / m for determining the Oxygen limit values according to test ASTM D 2863.70. The following mean values were obtained:

709821/0601

Dipl.-Ing. A. Spalthoff, patent attorney, 43 Essen physical appereance

Test piece from mixture A (without admixture):

the glass fiber appears white. An inhibition becomes noticeable at the fiber level.

Test piece from mixture B (with admixture):

the fiber is no longer visible on the surface, and there is no longer any whiteness along the fibers.

shrinkage

without leg amounts: mean shrinkage $ 0.85

with admixture of ground B ₂ O-: on average $ 0.50 the shrinkage in the test pieces with admixture is only 58 $ of the shrinkage in those without addition.

Losses when heating up

without admixture: average water loss $ 15.25 with admixture of B ^ O ,, ground: average $ 11.00 the water loss in the test pieces with admixture is only 725 * of the loss in those without addition.

Bending modulus E

without admixture: mean value of E 194.2

with addition of B ₂ O. ,, ground: on average 238.0 the flexural modulus E increases by $ 22.5.

Bending stress

without admixture: average 6.2

with the addition of BpO: an average of 6.5

bending stress increases by $ 5.

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Dipl.-Ing. A. Spalthoff, patent attorney, 43 Essen Oxygen limit value

without admixture ι 4-4-, 5

with addition of BpO,: 78

It is noteworthy that this limit value in the test pieces with admixture, i.e., this volume concentration from $ 78 oxygen at 22 # nitrogen to maintain the incineration is extraordinary under these conditions.

In addition, comparisons have been made regarding the behavior of a substrate or gel coat with phenolic laminates with and without the addition of ground BpCU.

For this purpose - this is not limiting here - polyesters based on HET acids with ßenzoyl peroxide as a catalyst and cobalt naphtenate as an accelerator were used to produce substrates or gel coat to which the laminates were applied: - either on the Based on Resophen PL 5 · 600, hardener ι ¹ 5.001, glass, without admixture;

- or based on Resophen PL 5 · 600, hardener P 5 glass, with the addition of Bp ⁰ ^ "

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Dipl.-Ing. A. Spalthoü, patent attorney, 43 Essen

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The former do not withstand if you make crossed scratches at a distance of 1m / m, while the latter one maintain correct adherence. This adherence is further improved, when adding 3 # boric anhydride to the gel coat.

The invention is not limited to the exemplary embodiments and types that have just been described, but rather extends also apply to every pneumatic, mechanical, electronic and analog process in which a deshydrating Addition at the stage of impregnation of the glass fibers (or another reinforcement) with the resin-hardener mixture he follows.

This general note is made easier to understand by the following, non-restrictive application examples:

1) In the process with wire-like rolling, the admixture is distributed over the resin-coated glass wire.

2) In a process with continuous impregnation and extrusion, the admixture is distributed at the impregnation point across the entire width of the fiberglass layer.

3) The addition takes place in a centrifugal process when the amplifier and the resin mixture settle inside the rotating mold.

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Dipl.-Ing. A. Spalthofi, patent attorney, 43 Essen

4) In a process with injection molding or die casting, the admixture takes place on the glass fiber reinforcement in the Mold before introducing the resin mixture.

5) It is also possible to add an admixture according to the invention in other embodiments of a type already known perform.

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Claims (7)

Dipl.-Ing. A. Spalthofi, patent attorney. 43 Essen 2646M5 claims 1. A process for the production of cast molded parts or articles based on phenolic resins or Reaol by simultaneous injection of at least one resin of the aforementioned type, reinforcing elements made of glass, and at least one acidic catalyst as main components in a mold, characterized in that one at the same time as the aforementioned main constituents are added at least one inorganic, anhydrous and hydrophilic compound, the amount of which is between 8 and 12 percent by weight of the liquid phenolic resin. 2. The method according to claim 1, characterized in that the inorganic, anhydrous, hydrophilic compound calcium semihydrate (SO ^ Ca) H ^ O is. ■ j>. Process according to Claim 1, characterized in that boric anhydride B ^ CU is used as the inorganic, anhydrous, hydrophilic compound. 4-, method according to claim 1 or 2, characterized in, that a semi-hydrogenated calcium sulfate is used as the inorganic, anhydrous, hydrophilic compound, which one obtained from sulfuric acid neutralized with milk of lime, the product obtained being filtered and washed out, and before use at a temperature of about 130 ° C 709821/0601 Dipl.-Ing. A. Spalthoff, patent attorney, 43 Essen 264614S is dehydrated. 5. Apparatus for performing the method according to claim 1 to 4, characterized in that it consists of: a pneumatically operated device for injecting the resin and the catalyst, which cooperates on the one hand with a glass fiber splitting and comminuting device coupled to pneumatic means, and on the other hand with associated electromagnetic and pneumatic means for feeding with deshydrating powder, the switching on and off of the three aforementioned units is controlled by an electrical relay device, which is also provided for regulating the powder throughput depending on the throughput of the other components. 6. The method according to any one of claims 1 to 4, characterized in that the inorganic, anhydrous, hydrophilic compound combined with any desired molding process that uses pneumatic, mechanical, electronic means or a combination of these means or analogous means, in the wetting stage the glass fibers (or another reinforcement) can be used through a mixture of resin and hardener. 7. Cast synthetic resin parts or articles with improved mechanical properties and better fire resistance, produced according to the method according to one of the claims 1 to 4 and 6 in a device according to claim 5 709821/0501